Method for preparing formamide compounds via hydrogenation of carbon dioxide catalyzed by porous materials

Patent metadata

Field	Value
Publication number	US-12371398-B2
Application number	US-202017754104-A
Country	US
Kind code	B2
Filing date	Dec 29, 2020
Priority date	Jan 24, 2020
Publication date	Jul 29, 2025
Grant date	Jul 29, 2025

Abstract

A method for preparing formamide compounds via hydrogenation of carbon dioxide catalyzed by porous materials includes the following steps: by taking porous organometallic polymers as catalysts, reacting amine compounds with carbon dioxide and hydrogen under an air atmosphere to prepare formamide compounds. The method has the advantages of high reaction efficiency, good selectivity, mild conditions, economy, environmental protection, and simple operation. The catalysts are solid organometallic polymers with large specific surface area, strong carbon dioxide adsorption, hierarchical pore distribution, and uniformly dispersed metal centers. They are designed and synthesized as the reaction catalysts by changing the proportion of the cross-linked comonomer. The catalysts can be especially used for catalytic synthesis of fine chemical N, N-dimethylformamide (DMF) without addition of any additional solvent, alkali, or other additives, which is convenient for separation and purification of DMF.

First claim

What is claimed is:

1. A method for preparing a formamide compound via hydrogenation of carbon dioxide catalyzed by porous materials, wherein a catalyst that is a porous organometallic polymer as shown in formula (V), and an organic amine compound, as shown in general formula (I), are reacted with carbon dioxide and hydrogen gas under an air atmosphere to form the formamide compound as shown in general formula (II);
the method comprises the following steps:
under the air atmosphere, adding the organic amine compound (I) and the catalyst (V) to a 125 mL autoclave, sealing the 125 mL autoclave, and charging the carbon dioxide and the hydrogen gas with a predetermined pressure to obtain a reaction system;
placing the reaction system in an oil bath, and then stirring and heating the reaction system to perform a reaction at a predetermined reaction temperature for a predetermined reaction time;
slowly releasing the pressure from the autoclave after cooling down, and obtaining the formamide compound by a distillation or a column separation;
wherein a reaction formula is:

wherein:
R 1 is selected from the group consisting of hydrogen, optionally substituted C 1 -C 20 alkyl, optionally substituted C 4 -C 10 cycloalkyl, optionally substituted C 6 -C 24 aryl, optionally substituted C 6 -C 24 heteroaryl, optionally substituted C 7 -C 25 aryl alkyl, optionally substituted C 7 -C 25 heteroaryl alkyl, —(CH 2 ) n —OR 3 , and —(CH 2 ) n —NR 4 R 5 , wherein n=1-8;
R 2 is selected from the group consisting of optionally substituted C 1 -C 20 alkyl, optionally substituted C 4 -C 10 cycloalkyl, optionally substituted C 6 -C 24 aryl, optionally substituted C 6 -C 24 heteroaryl, optionally substituted C 7 -C 25 aryl alkyl, optionally substituted C 7 -C 25 heteroaryl alkyl, —(CH 2 ) n —OR 3 , and —(CH 2 ) n —NR 4 R 5 , wherein n=1-8 and R 1 and R 2 are connected into the optionally substituted C 4 -C 10 cycloalkyl;
wherein R 3 , R 4 and R 5 are separately selected from the group consisting of hydrogen, optionally substituted C 1 -C 20 alkyl, optionally substituted C 6 -C 24 aryl, optionally substituted C 7 -C 25 aryl alkyl, and optionally substituted C 7 -C 25 heteroaryl, wherein R 4 and R 5 are connected into optionally substituted C 3 -C 10 cycloalkyl;
wherein substituted is selected from the group consisting of one or more hydrogens in the group substituted by a substituent selected from the group consisting of halogen, C 1 -C 4 alkyl, C 1 -C 4 halogenated alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -C 6 alkoxy, hydroxyl, amino, and sulfhydryl;
the porous organometallic polymer as shown in general formula (V) is:

wherein:

=(hetero)aryl and functional group substituted (hetero)aryl;
the N-heterocyclic carbene ligands are benzimidazolylidene, phenanthromidazolylidene, acenaphthoimidazolylidene, pyrenoimidazolylidene, or bibenzimidazolylidene ligands;
X is selected from the group consisting of halogen anion, tetrafluoroborate, hexafluorophosphate, and hexafluoroantimonate;
L is an auxiliary ligand, and the auxiliary ligand is selected from the group consisting of halogen, carbonyl, benzene ring, cyclopentene ring, cyclooctadiene, hydroxyl, water, carbonate, acetate, acetylacetone anion, and phosphine ligand;
R 1 and R 2 are separately selected from the group consisting of chain alkane groups with a carbon number of 1-12, a cyclic alkane group, benzyl, and aryl with a carbon number of 5-7;
the organic amine compound (I) is an organic primary amine compound or an organic secondary amine compound.

2. The method according to claim 1 , wherein a molar ratio of the organic amine compound (I) to the catalyst (V) is (1,000-100,000):1;
the predetermined reaction temperature is 80-150° C., and the predetermined reaction time is 2-160 hours.

3. The method according to claim 1 , wherein the predetermined pressure of the hydrogen gas is controlled at 5-40 atm, and the predetermined pressure of the carbon dioxide is controlled at 5-40 atm.

4. The method according to claim 1 , wherein the reaction is carried out in at least one organic solvent selected from the group consisting of: DMF, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, glycol dimethyl ether, tert-butyl methyl ether, benzene, methylbenzene, xylene, methanol, ethanol, isopropanol, and tert-butanol.

5. The method according to claim 1 , wherein when the organic amine compound (I) is dimethylamine or an equivalent dimethylamine carbon dioxide salt of the dimethylamine, the formamide compound is DMF.

6. The method according to claim 1 , wherein the catalyst (V) is recyclable and reusable.

7. The method according to claim 1 , wherein the porous organometallic polymer is prepared by a method comprising the following steps:
at a room temperature, obtaining a reaction mixture by dissolving in an organic solvent a bis-carbene iridium compound shown by general formula (III) and 3-9 equivalents of arene shown by general formula (IV), and slowly adding a cross-linking agent and a Lewis acid as catalysts under nitrogen conditions, and then sealing the reaction mixture;
placing the reaction mixture in an oil bath at 30-80° C. to perform a synthetic reaction for 1-72 hours until the synthetic reaction stops;
after cooling the reaction mixture, performing filtering, washing, Soxhlet extraction and vacuum drying to obtain the porous organometallic polymer shown by the general formula (V);
wherein a reaction formula is:

wherein:

=(hetero)aryl and functional group substituted (hetero)aryl;
the N-heterocyclic carbene ligands are benzimidazolylidene, phenanthromidazolylidene, acenaphthoimidazolylidene, pyrenoimidazolylidene, or bibenzimidazolylidene ligands;
X is selected from the group consisting of halogen anion, tetrafluoroborate, hexafluorophosphate, and hexafluoroantimonate;
L is the auxiliary ligand, and the auxiliary ligand is selected from the group consisting of halogen, carbonyl, benzene ring, cyclopentene ring, cyclooctadiene, hydroxyl, water, carbonate, acetate, acetylacetone anion, and phosphine ligand;
R 1 and R 2 are separately selected from the group consisting of the chain alkane groups with the carbon number of 1-12, and the cyclic alkane groups, benzyl, and aryl with the carbon number of 5-7.

8. The method according to claim 7 ,
wherein a mass ratio of the arene shown by the general formula (IV) to the bis-carbene iridium compound shown by the general formula (III) is (1-24):1;
a mass ratio of the cross-linking agent to the bis-carbene iridium compound shown by the general formula (III) is (1-100):1.

9. The method according to claim 8 , wherein
the cross-linking agent is selected from the group consisting of: dimethoxymethane, trimethyl orthoformate, trimethyl orthoacetate, triethyl orthoformate, triisopropyl orthoformate, dichlorobenzene, dibromobenzene, 1,4-dibenzyl chloride, 1,4-dibenzyl bromide, and carbon tetrachloride;
the organic solvent is selected from the group consisting of dichloromethane, chloroform, carbon tetrachloride, and 1,2-dichloroethane; and
the Lewis acid

Assignees

• Univ Fudan

Inventors

• Tu Tao
• Shen Yaliang
• Zheng Qingshu

Classifications

• C07F15/0033

  Iridium compounds · CPC title

• B01J2531/827

  Iridium · CPC title

• B01J2231/40

  Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions · CPC title

• B01J31/2273

  with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes · CPC title

• B01J31/20

  Carbonyls · CPC title